EP4280332A1 - Composition polyélectrolytique et ses procédés de préparation - Google Patents

Composition polyélectrolytique et ses procédés de préparation Download PDF

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Publication number
EP4280332A1
EP4280332A1 EP23173490.6A EP23173490A EP4280332A1 EP 4280332 A1 EP4280332 A1 EP 4280332A1 EP 23173490 A EP23173490 A EP 23173490A EP 4280332 A1 EP4280332 A1 EP 4280332A1
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EP
European Patent Office
Prior art keywords
styrene
bis
para
ortho
lithium
Prior art date
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EP23173490.6A
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German (de)
English (en)
Inventor
Bert KRUTZER
Jiaqi YAN
Vijay Mhetar
Roger TOCCHETTO
Carl Willis
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Kraton Polymers Nederland BV
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Kraton Polymers Nederland BV
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Publication of EP4280332A1 publication Critical patent/EP4280332A1/fr
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0082—Organic polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0085—Immobilising or gelification of electrolyte
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the disclosure relates to a polyelectrolyte composition comprising a polyionic multiblock polymer, methods of preparation, and applications thereof.
  • Li-ion batteries have been widely used in various devices due to their multiple advantages. However, industries are still working on developing next generation Li-ion batteries with improved performance.
  • One of the ways to improve the performance of Li-ion batteries is to use effective electrolytes, e.g., ionic liquids (ILs).
  • ILs are attractive electrolytes having interesting properties, such as, for example, high ion conductivity, thermal stability, non-flammability, high heat capacity, negligible volatility at room temperature, strong polarizability, etc.
  • Polymers containing ILs or poly(ionic liquid)s are a special type of polyelectrolytes which contain ILs associated with selected repeating units in the polymer chain. ILs are in a liquid state at room temperature, whereas PILs are solid and thus, can be made as polyelectrolytes having many advantages, e.g., no leakage, high (thermal) stability, cyclability (lifetime), overall storage capacity, etc.
  • Styrenic block copolymers are well known in the art and can be functionalized to modify their characteristics. Incorporation of ILs in selected blocks of the SBC can lead to the formation of polyelectrolytes. However, the performance of such polyelectrolytes depends on block contents of SBC, type of ILs, concentration of ions, etc.
  • a polyelectrolyte composition comprises, consists essentially of, or consists of (a) a polyionic multiblock polymer containing a styrenic block copolymer precursor with at least a quaternary ammonium salt, the styrenic block copolymer precursor comprises: a block D derived from a substituted vinyl aromatic monomer, having a molecular weight (M p ) of 10 to 100 kg/mol, a block A derived from a vinyl aromatic monomer, having a molecular weight (M p ) of 5 to 100 kg/mol, and optionally a block B derived from a conjugated diene monomer, having a molecular weight (M p ) of 1 to 40 kg/mol; (b) a cross-linking agent comprising a compound having at least two amino groups, wherein the cross-linking agent is present in an amount of 0.05 to 20 mol%, based on total mol of the quaternary ammonium salt, the
  • the cross-linking agent is present in an amount of 0.1 to 15 mol%, based on total mol of the quaternary ammonium salt.
  • the cross-linking agent is selected from the group consisting of 1,4-bis(imidazol-1-yl)-butane, 1,4-Bis(2-methyl-1H-imidazol-1-yl)butane, 1,4-bis(2-phenylimidazol)butane, 1,6-diimidazolehexane, 1,6-bis(2-ethylimidazolyl)butane, 1,6-bis(2-phenylimidazol)butane, 1,8-diimidazoleoctane, 1,8-bis(2-ethylimidazolyl)butane, 1,8-bis(2-phenylimidazol)butane, 1,10-diimidazoledecane, 1,10-bis(2-ethylimidazolyl)butane, and 1,10-bis(2-phenylimidazol)butane, and mixtures thereof.
  • the polyelectrolyte composition has a conducting phase containing a combination of the lithium salt and the ionic liquid, and wherein a volume fraction of the conducting phase is 0.5 to 0.8, based on total volume of the polyelectrolyte composition.
  • At least one of [a group such as A, B, and C]" or “any of [a group such as A, B, and C]” means a single member from the group, more than one member from the group, or a combination of members from the group.
  • at least one of A, B, and C includes, for example, A only, B only, or C only, as well as A and B, A and C, B and C; or A, B, and C, or any other all combinations of A, B, and C.
  • Polystyrene content or PSC of a block copolymer refers to the weight % of vinyl aromatic, e.g., styrene in the block copolymer, calculated by dividing the sum of molecular weight of all vinyl aromatic units by the total molecular weight of the block copolymer.
  • PSC can be determined using any suitable methodology such as proton nuclear magnetic resonance (NMR).
  • Molecular weight refers to the polystyrene equivalent molecular weight in g/mol or kg/mol of a polymer block or a block copolymer. Molecular weight can be measured with gel permeation chromatography (GPC) using polystyrene calibration standards, such as is done according to ASTM 5296.
  • the GPC detector can be an ultraviolet or refractive index detector or a combination thereof.
  • the chromatograph is calibrated using commercially available polystyrene molecular weight standards. Molecular weight of polymers measured using GPC so calibrated are polystyrene equivalent molecular weights or apparent molecular weights. Molecular weight expressed herein is measured at the peak of the GPC trace and are commonly referred to as polystyrene equivalent "peak molecular weight," designated as M p .
  • Ionic liquid or IL refers to a salt in the liquid state in which ions are poorly coordinated. Ionic liquids are also called liquid electrolytes, ionic melts, ionic fluids, fused salts, liquid salts, or ionic glasses.
  • Ionic conductivity refers to a measurement of a substance's tendency towards ionic conduction. This involves the movement of ions.
  • Polyelectrolyte refers to a polymer whose repeating units (some or all) bear an electrolyte group.
  • Li-ion battery refers to a lithium based energy storage system, but as used herein, the term also includes applications of other materials such as sodium, potassium, etc., for use in energy storage system.
  • the term Li-ion battery can be interchangeably used as Li-ion cell or cell or coin cell.
  • Constant current (CC) charging refers to the use of a constant current to charge the battery for the whole charging process.
  • Constant current constant voltage (CC-CV) charging refers to the charging where a predetermined voltage is used to charge the battery followed by CC charging, e.g., 4.2 V for 1 hour used as formation prior to cycling.
  • Charging capacity refers to a capacity obtained by the constant current charging at a current value until a certain cell voltage is reached.
  • Discharge capacity refers to discharging of the cell at a current value until the cell voltage reaches a certain value.
  • the present disclosure relates to a polyelectrolyte composition
  • a polyelectrolyte composition comprising a polyionic multiblock polymer (PILSBC) containing a styrenic block copolymer (SBC) precursor having at least a quaternary ammonium salt, a cross-linking agent, an ionic liquid (IL), and a salt selected from lithium salt, sodium salt, and mixtures thereof.
  • PILSBC polyionic multiblock polymer
  • SBC styrenic block copolymer
  • IL ionic liquid
  • the polyelectrolyte composition provides improved ionic conductivity, electrochemical properties, and can be processed into thin films / membranes for use in batteries, e.g., a Li-ion battery.
  • the PILSBC comprises a styrenic block copolymer (SBC) precursor having at least a quaternary ammonium salt (QAS), and a cross-linking agent with at least two amino groups.
  • SBC precursor can be any of linear or branched (multi-armed) block copolymer having at least a block D derived from a substituted vinyl aromatic monomer; a block A derived from a vinyl aromatic monomer; and optionally a polymer block B derived from a conjugated diene monomer.
  • the SBC precursor has a configuration selected from A-D, D-B, D-A-D, A-D-A, D-B-D, D-B-A, D-A-B, A-D-B, (A-D) n X, (D-B) n X, (D-A-D) n X, (A-D-A) n X, (D-B-D) n X, (D-B-A) n X, (D-A-B) n X, (A-D-B) n X, (A-D-B) n X, A-B-D, A-D-B, A-D-D, A-D-B, A-B-D-B', D-B-A-B', A-B-D-A, A-D-B-A, A-B-D-B'-A, A-D-B-D-A, A-B-A-D-A, A-D-A-B
  • the SBC can be hydrogenated, unhydrogenated, partially hydrogenated or selectively hydrogenated.
  • each vinyl aromatic monomer and substituted vinyl aromatic monomer is introduced or copolymerized into the diene block by any order and in any distribution to form any of configurations described above.
  • the substituted vinyl aromatic monomer has a substitution on any of ortho, meta, or para position of an aromatic ring.
  • the substitution is at least one selected from the group consisting of alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, hetercycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, and mixtures thereof.
  • the substituted vinyl aromatic monomer is selected from the group consisting of alkyl substituted styrene, ortho-alkyl substituted styrene, para-alkyl substituted styrene, ortho, para-dialkyl substituted styrene, and mixtures thereof.
  • alkyl substituted styrene monomers include ortho-methyl styrene, ortho-ethyl styrene, ortho-n-propyl styrene, ortho-iso-propyl styrene, ortho-n-butyl styrene, ortho-iso-butyl styrene, ortho-sec-butyl styrene, ortho-tert-butyl styrene, ortho-decyl styrene, isomers of ortho-dodecyl styrene, para-methyl styrene, para-ethyl styrene, para-n-propyl styrene, para-iso-propyl styrene, para-n-butyl styrene, para-iso-butyl styrene, para-sec-butyl styrene, para-
  • the vinyl aromatic monomer is selected from the group consisting of styrene, alpha-methylstyrene, and mixtures thereof.
  • the conjugated diene monomer is selected from the group consisting of 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1-phenyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 3-butyl-1,3-octadiene, myrcene, farnesene, 1,3-cyclohexadiene, piperylene, and mixtures thereof.
  • each block A has a molecular weight (M p ) of 5 - 100, or 10 - 90, or 15 -80, or 5 - 50, or 10 - 50 kg/mol.
  • each block B and B' independently has a molecular weight (M p ) of 1 - 40, or 2 - 35, or 5 - 30, or 5 - 25, 2 - 20, or > 2, or ⁇ 25 kg/mol.
  • each block D has a molecular weight (M p ) of 10 - 100, or 10 - 90, or 15 -70, or 5 - 55, or 15 - 60 kg/mol.
  • the SBC precursor has a molecular weight (M p ) of 20 - 400, or 25 - 350, or 30 -300, or 35 - 250, or 40 - 200, 20 - 150, or 25 - 130, or 30 - 120, or 30 - 130 kg/mol.
  • the SBC precursor has a polystyrene content (PSC) of 5 - 70, or 5 - 50, or 5 - 40, or > 5, or ⁇ 75 wt.%, based on total weight of the SBC precursor.
  • PSC polystyrene content
  • each block B and B' before hydrogenation, has a vinyl content of 5 - 35, or 8 - 30, or 10 - 25, or 12 - 20, or > 10, or ⁇ 30 wt.%, based on weight of the polymerized conjugated diene monomer in each block B and B'.
  • each block A and D is essentially left non-hydrogenated.
  • Each block A and D can independently have a hydrogenation level of ⁇ 30, or ⁇ 20, or ⁇ 10, or ⁇ 5 mol%, based on mol of the polymerized monomer in each block A and D.
  • each block B and B' is hydrogenated to a hydrogenation level of > 80, or > 85, or > 90, or > 95, or > 98, or > 99 or up to 100 mol%, based on total mol of the polymerized conjugated diene monomer in each block B and B'.
  • the hydrogenation level refers to the % of original unsaturated bonds which become saturated upon hydrogenation, which can be determined using UV-VIS spectrophotometry and / or proton NMR and / or via ozonolysis titration.
  • combined blocks B and B' if present, constitute up to 20 wt.%, or 1 - 18, or 2 - 15, or > 1.5, or ⁇ 15 wt.%, based on total weight of the SBC precursor.
  • the QAS is bonded to at least one of the blocks A, B, and D.
  • the block D has at least one QAS and each block A and B is substantially free of the QAS.
  • the block B has at least one QAS and each block A and D is substantially free of the QAS.
  • each block B and D has at least one QAS and the block A is substantially free of the QAS.
  • the cross-linking agent comprises a compound containing at least two amino groups.
  • the cross-linking agent is selected from the group consisting of 1,4-bis(imidazol-1-yl)-butane, 1,4-Bis(2-methyl-1H-imidazol-1-yl)butane, 1,4-bis(2-phenylimidazol)butane, 1,6-diimidazolehexane, 1,6-bis(2-ethylimidazolyl)butane, 1,6-bis(2-phenylimidazol)butane, 1,8-diimidazoleoctane, 1,8-bis(2-ethylimidazolyl)butane, 1,8-bis(2-phenylimidazol)butane, 1,10-diimidazoledecane, 1,10-bis(2-ethylimidazolyl)butane, and 1,10-bis(2-phenylimidazol)butane, and mixtures thereof.
  • cross-linking agents based on bi-imidazole examples include 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyl-biimidazole, 2,2'-bis(o-fluorophenyl)-4,4',5,5'-tetraphenyl-biimidazole, 2,2'-bis(o-methylphenyl)-4,4',5,5'-tetraphenyl-biimidazole, 2,2'-bis(o-methoxyphenyl)-4,4',5,5'-tetraphenyl-biimidazole, 2,2'-bis(o-ethylphenyl)-4,4',5,5'-tetraphenyl-biimidazole, 2,2'-bis(p-methoxyphenyl)-4,4',5,5'-tetraphenyl-biimidazole, 2,2'-bis(2,2',4,
  • cross-linking agents based on diamine can be used, e.g., diamine 4,4'-methylene-bis-(o-chloroaniline), dimethyl thio-toluene diamine, 3,5-diethyltoluene-2,4-diamine, 3,5-diethyltoluene-2,6-diamine, diethyl toluenediamine, methylenedianiline, di(4-aminocyclohexyl)methane, isophoronediamine, 1,3-xylylenediamine, diethylenetriamine, triethylenetetramine, 4-(4'-aminobenzyl)cyclohexylamine, hexamethylenediamine, [3-(trimethoxysilyl)propyl]-ethylenediamine, N,N'-dicinnamylidene-1,6-hexanediamine, 2-methyl-1,5-pentanediamine, 1,2-diaminocyclohex
  • Examples of other amines as cross-linking agents include hexamethylenetetramine, triethylenetetramine, tetraethylenepentamine, tetraethylenepentamine, iminobispropylamine, bis(hexamethylene)triamine, 1,3,6-trisaminomethylhexane, diethylaminopropylamine, tetramethylguanidine, 2-(dimethylaminomethyl)phenol, 2,4,6-tris(dimethylaminomethyl)phenol, N2,N2,N4,N4,N6,N6-hexaallyl-1,3,5-triazine-2,4,6-triamine, N-aminoethyl piperazine, N-amino-N'-methylpiperazine, bis (hexamethylene) triamine, 1,3,6-trisaminomethylhexane, N-aminoethylpiperazine, pentaethylene hexamine, dipropylene triamine, tributylene t
  • the cross-linking agent has a general formula (I), R 10 is a hydrogen atom, an aliphatic hydrocarbon of C 1 - C 10 , a phenyl group, or a substituted phenyl group with substitution of C 1 -C 5 hydrocarbon, and p is from 1 to 10.
  • the cross-linking agent is in amounts of 0.05 - 20, or 0.1 - 15, or 0.1 - 10, or 0.2 - 10, or 0.3 - 5, or 0.5 - 10, or ⁇ 10, or > 0.1 mol%, based on total mol of the QAS present in the SBC precursor.
  • the PILSBC is prepared by first making the SBC precursor as disclosed in U.S. Patent No. 7449518 .
  • the SBC precursor is prepared by an anionic polymerization or by a sequential (or successive) polymerization of the monomers in solution in the presence of an initiator, followed by terminating the polymerized block copolymer chains.
  • the polymerization of monomers can be performed by stepwise addition of monomers to the solution containing the initiator, followed by coupling of the resulting sequential block copolymer chains with the coupling agent (if present).
  • the process conditions for the sequential polymerization steps are similar to those used for anionic polymerizations, at a temperature of -30 to 150°C, or 10 to 100°C, or 30 to 90°C.
  • the polymerization can be carried out in an inert atmosphere, e.g., nitrogen, or pressure in the range of 0.5 - 65 bars.
  • the polymerization generally requires ⁇ 12 hrs., or from 5 min. to 5 hrs., depending on factors including temperature, concentration of monomer components, the molecular weight of the target polymer, etc.
  • the coupling agent is selected from the group consisting of di- or multi-vinylarene compounds; di- or multi-epoxides; di- or multi-isocyanates; di- or multi-alkoxysilanes; di- or multi-imines; di-or multi-aldehydes; di- or multi-ketones; alkoxytin compounds; di- or multi-halides, such as silicon halides and halosilanes; mono-, di-, or multi-anhydrides; di- or multi-esters, such as the esters of monoalcohols with polycarboxylic acids; diesters which are esters of monohydric alcohols with dicarboxylic acids; diesters which are esters of monobasic acids with polyalcohols such as glycerol; silanes; and mixtures thereof.
  • any effective amount of the coupling agent is employed to obtain a desired coupling efficiency, e.g., > 50%, or > 60%, or > 70%, or > 80%, or > 90%, or ⁇ 99%.
  • the PILSBC is obtained by introducing the QAS functionality post-polymerization or during the preparation of the SBC precursor by using a monomer containing the QAS, e.g., vinylbenzylamino functionality.
  • the PILSBC is obtained by using at least one monomer containing QAS functionality for polymerization, e.g., vinyl aromatic monomer, substituted vinyl aromatic monomer, or conjugated diene monomer.
  • a post-polymerization step is employed to introduce or add more functional group(s), either same or different than existing functional group.
  • the block D or the block B is functionalized to have the QAS.
  • the block D is functionalized to have the QAS by first halogenating the block D using at least one halogenating agent, e.g., a brominating agent, chlorinating agent, and the like.
  • the SBC precursor is dissolved in a suitable solvent at 50 - 100°C and to this solution, the halogenating agent, e.g., N-bromosuccinimide (NBS) and an initiator are added, and the reaction content is stirred for 20 - 80 min, to obtain a brominated SBC (Br-SBC) precursor.
  • NBS N-bromosuccinimide
  • the solvent can be selected from halogenated aromatic compounds, e.g., chlorobenzene.
  • the initiator can be free radical initiators, e.g., azobisisobutyronitrile (AIBN), 4,4'-azobis(4-cyanovaleric acid), 1,1'-azobis(cyclohexanecarbonitrile), 2,2'-azobis(2-methylpropionamidine) dihydrochloride, etc.
  • the SBC precursor has a degree of halogenation of 20 - 90, or 25 - 85, or 30 - 80, or 30 - 70 mol%, based on total mol of the SBC precursor.
  • the PILSBC is a bromide ion conducting polymer obtained by quaternization of the Br-SBC precursor with at least a quaternizing agent, e.g., a nitrogen containing heterocyclic compound such as 1-methylimidazole.
  • a quaternizing agent e.g., a nitrogen containing heterocyclic compound such as 1-methylimidazole.
  • cross-linking is carried out after quaternization of the halogenated-SBC precursor.
  • quaternization and cross-linking are performed concurrently in-situ.
  • quaternization and cross-linking are achieved by dissolving the halogenated-SBC precursor in an aromatic hydrocarbon solvent, e.g., toluene, at room temperature and adding the quaternizing agent, the cross-linking agent, and an alcohol into the dissolved halogenated-SBC precursor to obtain a cross-linked PILSBC in liquid form.
  • the alcohol include methanol, ethanol, propanol, and the like.
  • the cross-linked PILSBC can be made into a film by methods known in the art, before the next step, the ion-exchange step can be performed with ionic liquid and lithium salt.
  • the cross-linked PILSBC has a level of quaternization of up to 100, or 40 - 98, or 50 - 95, or 60 - 90, or 40 - 75 mol%, based on total mol of the halogenated units in the SBC precursor.
  • IL comprises at least a cation and at least an anion.
  • cations include tetraalkylammonium, di-, tri-, and tetra-alkylimidazolium, alkylpyridinium, dialkyl-pyrrolidinium, dialkylpiperidinium, tetraalkylphosphonium, and trialkylsulfonium.
  • Examples of anions include PF 6 - , ClO 4 - , CF 3 SO 3 - , C 4 F 9 SO 3 - , BF 4 - , B(CN) 4 - , CH 3 BF 3 - , CF 3 BF 3 - , C 2 F 5 BF 3 - , CF 3 CO 2 - , CF 3 SO 3 - , N(COCF 3 ) (SO 2 CF 3 ) - , N(SO 2 F) 2 - , C(CN) 3 - , SCN - , SeCN - , F(HF) 2.3 - , (CF 3 SO 2 ) 2 N - , (C 2 F 5 SO 2 ) 2 N - , (CF 3 SO 2 ) 3 - , C - , AsF 6 - , SO 4 2- , (CN) 2 N - , and NO 3 - .
  • the anion can be based on an organic acid, e.g., R 3 SO 3 - , R 4 CO 2 - , R 5 BF 3 - , wherein R 3 , R 4 , and R 5 are an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, an aralkenyl group having 8 to 14 carbon atoms.
  • an organic acid e.g., R 3 SO 3 - , R 4 CO 2 - , R 5 BF 3 - , wherein R 3 , R 4 , and R 5 are an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, an aralkenyl group having 8 to 14 carbon atoms.
  • IL is selected from the group consisting of ethylmethylimidazolium bis(trifluoromethanesulfonyl)imide (EMITFSI), ethylmethylimidazolium bis(pentafluoroethanesulfonyl)imide (EMIPFSI), butylmethylimidazolium bis(trifluoromethanesulfonyl)imide (BMITFSI), butylmethylimidazolium bis(pentafluoroethanesulfonyl)imide (BMIPFSI), 1-butyl-3-methylimidazolium tetrafluoroborate ([Bmim][BF4]), N-butyl-N31 methylpyrrolidinium bis(3 trifluoromethanesulfonyl)imide (PYR14+TFSI-I), trihexyl(tetradecyl)phosphoniumdicyanamide [P 6,6,6,14
  • the polyelectrolyte composition comprises IL in a suitable amount to obtain a mol ratio of IL to the QAS of the SBC precursor (QAS present in the SBC precursor) of 0.1:1 - 1:1, or 0.15:0.95 - 0.2:0.80, or 0.25:0.75 - 0.3:0.65, or 0.35:0.6 - 0.40:0.55, or > 0.25, or ⁇ 0.85.
  • the polyelectrolyte composition contains IL in an amount of 0.05 - 1 equivalents of IL per 1 equivalent of the QAS of the SBC precursor (QAS present in the SBC precursor).
  • the amount of IL added can be of 0.1 - 0.95, or 0.15 - 0.90, or 0.2 - 0.85, or 0.25 - 0.8, 0.3 - 0.75, or > 0.20, or ⁇ 0.95, per 1 equivalent of the QAS of the SBC (QAS present in the SBC precursor).
  • lithium salt examples include lithium bis(trifluoromethane)sulfonimide (Li-TFSI), lithium hexafluorophosphate (Li-PF6), lithium perchlorate (LiClO4), lithium borofluoride (LiBF4), lithium hexafluoroarsenide (LiAsF6), lithium trifluoro-metasulfonate (LiCF3SO3), bis-trifluoromethyl sulfonylimide lithium (LiN(CF3SO2)2, lithium bis(oxalato)borate (LiB(C2O4)2), lithium oxalyldifluoroborate (LiBF2C2O4), lithium nitrate (LiNO3), Li-fluoroalkyl-phosphates (LiPF3(CF2CF3)3), lithium bisperfluoroethysulfonylimide (LiBETI), lithium thiocyanate (LiSCN), lithium dicyanamide
  • the polyelectrolyte composition comprises a salt other than the lithium salt.
  • salt other salts include sodium salts, ammonium salts, magnesium salts, potassium salts, calcium salts, salts based on iron phosphate, salts of silver, salts of barium, salts of lead, and mixtures thereof.
  • the polyelectrolyte composition comprises the lithium salt in a suitable amount so to obtain a mol ratio of the lithium salt to the QAS of the SBC precursor (QAS present in the SBC precursor) of 5:1 - 20:1, or 6:1 - 18:1, or 8:1 - 15:1, or 10: 1 - 12: 1, or > 8: 1, or ⁇ 18: 1.
  • the polyelectrolyte composition further comprises at least an additive selected from the group consisting of activators, curing agents, crosslinking agents different from diamine based, stabilizers, neutralizing agents, thickeners, coalescing agents, slip agents, release agents, antiozonants, color change pH indicators, plasticizers, tackifiers, film forming additives, dyes, pigments, UV stabilizers, UV absorbers, fillers, other resins, redox couples, flame retardants, viscosity modifiers, wetting agents, deaerators, toughening agents, colorants, heat stabilizers, light stabilizers, lubricants, flow modifiers, drip retardants, antiblocking agents, antistatic agents, processing aids, stress-relief additives, binding agents, and mixtures thereof.
  • an additive selected from the group consisting of activators, curing agents, crosslinking agents different from diamine based, stabilizers, neutralizing agents, thickeners, coalescing agents, slip agents, release agents, antiozonants, color
  • the additive is used in amounts of up to 10 wt.%, or 0.1 - 10, or 0.5 - 5, or 1 - 10, or 1 - 5 wt.%, based on total weight of the polyelectrolyte composition.
  • the polyelectrolyte composition further comprises a polymer other than the cross-linked PILSBC.
  • the polymer include poly(acrylamides), polyolefins, polyesters, polyethylene terephthalates, polybutylene terephthalates, poly(butyl succinates), polycarbonates, polyetherimides, polyphenyloxides (PPOs), polystyrenes, poly(methyl methacrylates), poly(n-vinyl-pyrrolidone), polyethylenimene, poly(dimethyl acrylamide), polyether ketone ketone (PEKK), polytetrafluoroethylene (PTFE), polyamide (PA), polyimide (PI), polyacrylate, poly(dimethylsiloxane), and mixtures thereof.
  • the polymer is added in amounts of 1 - 30, or 2 - 20, or 1 - 15, or 1 - 10, or 5 - 25 wt.%, based on total weight of the polyelectrolyte composition.
  • the cross-linked PILSBC is mixed with Li salt and IL having a suitable mol ratio, for a suitable period, then made into a film / membrane / coating.
  • a cross-linked PILSBC film is soaked in a mixture of Li salt and IL having a suitable mol ratio, for a period of 1 - 40 hrs., or 5 - 30 hrs., or 10 - 35 hrs. After soaking the film into the mixture of the Li salt and IL, the Li salt and IL are adsorbed onto the cross-linked PILSBC film, resulting in the formation of a polyelectrolyte film.
  • the cross-linked PILSBC has a cross-linking percentage of 0.1 - 50%, or 0.5 to 30%, or 1 - 25%, or 0.1 to 20%, or 0.5 to 30%.
  • Li salt and IL having a suitable mol ratio is added directly to a cross-linked PILSBC in liquid form, then the solution is made into a film by any of solvent casting, coating, dipping, etc., to obtain a film after evaporation of any added solvent.
  • solvents for the preparation of polyelectrolyte composition and film thereof include acetone, acetyl acetone, acetic acid, acetonitrile, benzonitrile, 1-butanol, 2-butanol, 2-butanone, t-butyl alcohol, benzyl alcohol, cyclohexane, cyclohexanol, cyclohexanone, dichloromethane, 1,2-dichloroethane, diethylene glycol, diethyl ether, diglyme (diethylene glycol dimethyl ether), 1,2-dimethoxy-ethane (glyme, DME), 1,4-dioxane, methanol, ethanol, 1-propanol, 2-propanol (isopropanol), methyl acetate, ethyl acetate, ethyl acetoacetate, butyl acetate, ethylene glycol, glycerin, heptane, he
  • the polyelectrolyte composition is made into films having a thickness of 10 - 200 ⁇ m, or 15 - 180 ⁇ m, or 20 - 150 ⁇ m, or 25 - 100 ⁇ m, or 10 - 80 ⁇ m, or 15 - 50 ⁇ m.
  • the polyelectrolyte composition is deposited on an electrode (anode and / or cathode) by any of solvent casting, coating, dipping process, etc., to obtain a film of polyelectrolyte composition on the electrode.
  • the film coated electrode employed in assembling a Li battery or cell.
  • the Li salt and IL forms a conducting phase in the polyelectrolyte composition.
  • the polyelectrolyte composition has a volume fraction of the conducting phase of 0.15 - 0.85, or 0.25 - 0.80, or 0.35 - 0.80, or 0.5 - 0.8, or 0.52 - 0.78, or 0.54 - 0.75, or 0.55 - 0.72, or 0.58 - 0.7, based on total volume of the polyelectrolyte composition; alternatively, a volume fraction of the cross-linked PILSBC in the polyelectrolyte composition is from 0.20 - 0.50, or 0.22 - 0.48, or 0.25 - 0.46, or 0.28 - 0.45, or 0.30 - 0.42, based on total volume of the polyelectrolyte composition.
  • the volume fraction of the conducting phase can be computed from the volume(s) of the Li salt, IL, and the cross-linked PILSBC, each volume value is computed based on the amounts (in weight) of each of Li salt, IL, and the cross-linked PILSBC, and the respective density value.
  • a film obtained from the polyelectrolyte composition can selectively transport anions, water, and gases, easy for handling, shaping, and forming into a pattern.
  • the film is ionically conductive and electrically non-conductive.
  • a film when used in Li-ion batteries exhibits suppression growth of Li dendrimers, and helps avoiding short out.
  • the film can simplify the process of assembling Li-ion battery, obviating a spacer to separate electrodes. Due to the solid nature of electrolytes (i.e., polyelectrolyte composition), Li-ion batteries can be prepared into variety of shapes and forms, and a rigid case is not needed to carry liquid electrolytes.
  • the film has an ionic conductivity at 30°C of 1.50 x 10 -9 - 2.0 x 10 -4 , or 2.0 x 10 -9 - 1.0 x 10 -4 , or 8.0 x 10 -8 - 9.0 x 10 -5 , or 6.0 x 10 -8 - 9.0 x 10 -5 or 5.0 x 10 -8 - 8.5 x 10 -5 , 2.5 x 10 -6 - 1.0 x 10 -3 , or 5.0 x 10 -6 - 1.5 x 10 -3 , or 1.0 x 10 -5 - 2.0 x 10 -3 , or > 2.0 x 10 -6 , or > 4.0 x 10 -6 S cm -1 .
  • the film of polyelectrolyte composition when used in a battery / cell shows excellent discharge capacity.
  • a Li-ion battery containing the polyelectrolyte film has an electrochemical stability of 1 - 12 V, or 2 - 10 V, or 2.5 - 8V, or 3 - 6 V, or 3.5 - 5.5V, or 4 - 7V, or > 4V, or ⁇ 10 V.
  • Electrochemical stability refers to a control of an open circuit voltage of the polymer electrolyte.
  • the Li-ion battery has a retention capacity of > 80%, or > 85%, or > 90%, or > 95%, or > 97%, or ⁇ 99.5%, after at least 1000 charge / discharge cycles at room temperature with respect to the first cycle.
  • the retention capacity of the Li-ion battery refers to a full charge or discharge capacity of a battery obtained after the battery is used for a certain period or left unused for a prolonged period.
  • the polyelectrolyte composition can be used in the preparation of anionic exchange membrane (AEM), solid ionic conductors, powerful dispersant and stabilizer, actuator, absorbent, precursor for carbon materials, electrolyte for batteries (Li-ion or Na-ion), membrane for fuel cells, membrane for capacitive deionization (CDI), membrane for electrolysis cells, membrane for STP (sewage treatment plan), pervaporation membrane, reverse osmosis membrane, forward osmosis membrane, energy recovery membrane, evaporative cooling applications, humidifiers, carrier / dispersant for inorganic salts, rheology modifier, anti-fungal composition, anti-bacterial composition, etc.
  • AEM anionic exchange membrane
  • solid ionic conductors solid ionic conductors, powerful dispersant and stabilizer, actuator, absorbent, precursor for carbon materials
  • electrolyte for batteries Li-ion or Na-ion
  • membrane for fuel cells membrane for capacitive deionization (CDI)
  • CDI capacitive
  • the film has applications in an electrolyzer to conduct protons from the anode to the cathode while insulating the electrodes electrically.
  • the electrolyzer containing the film electrolyzes water to generate oxygen gas and hydrogen gas.
  • Ionic conductivity is measured by electrochemical impedance spectroscopy (EIS) with an impedance analyzer combined with potentiostat / galvanostat.
  • EIS electrochemical impedance spectroscopy
  • a film sample of polyelectrolyte composition in a circular shape having a size of about 1.13 cm 2 is placed between two stainless steel solid blocking electrodes encapsulated by a Teflon holder.
  • heat from 20 to 100°C is applied to stainless steel blocking electrodes by heating tape.
  • Impedance spectra are collected for frequencies in the range of 1 MHz to 0.1 Hz with an AC (alternate current) perturbation of 10 mV at open circuit potential at a temperature range from 30 to 100°C. Films are held at each temperature for 1 hr.
  • ⁇ L/(AR), where L is the thickness of the film, A is the cross-sectional area of the blocking electrode (ca. 1.2161 cm 2 ), and R is the resistance of the film determined by the equivalent circuit regression of the Nyquist data.
  • the components used in examples include:
  • the block D was brominated by dissolving about 10 g of SBC precursor in about 190 g of chlorobenzene solvent to prepare a mixture.
  • the mixture was heated at 70°C for 30 minutes and about 1.5 g of N-bromosuccinimide and 0.06 g of azobisisobutyronitrile (AIBN) were added dropwise with stirring.
  • the reaction was continued for another 30 minutes to obtain brominated block D or brominated SBC (Br-SBC) precursor.
  • Functionalization of the Br-SBC precursor was conducted by dissolving in a suitable amount in about 40 ml of toluene to obtain a homogenous solution.
  • Preparation of polyelectrolyte compositions and films thereof PILSBC (without cross-linking), Li salt, and IL liquid (in DMAc) were mixed in suitable amounts in DMAc and a solution of polyelectrolyte composition was obtained.
  • Pre-film was obtained by casting polyelectrolyte composition onto a silicon coated PET film and allowed to evaporate maximum solvent. Dried pre-film (containing PILSBC without cross-linking) was then dissolved in DMAc to obtain concentration of about 20 %.
  • Li salt Li-TFSI
  • EMI-TFSI IL
  • the mol ratio of Li salt to block D containing QAS (in PILSBC) was kept constant at 0.1.
  • the mol ratio of IL to block D containing QAS was varied (termed as "r") as shown in table 2.
  • the ternary solution was used to obtain a polyelectrolyte film by casting ternary solution onto a silicon coated PET film via doctor blade using an automatic film applicator. The film was dried under vacuum at ambient temperature for about 24 hours and then at 120°C for about 48 hours to remove residual solvent to obtain film of polyelectrolyte composition.
  • a cathode was prepared by dispersing 80 wt.% of NMC811 (a composition with 80 wt.% of nickel, 10 wt.% of manganese, and 10 wt.% of cobalt), 10 wt.% of carbon black, and 10 wt. % of PVDF in N-methyl-2-pyrrolidone and casting this cathode slurry onto a C-Al foil (copper-Al foil) using the film applicator.
  • the cathode was dried at ambient conditions overnight followed by drying at 120°C under vacuum for about 6 hours to remove the residual solvent and obtain the cathode.
  • Li / polyelectrolyte film / NMC811 cells were assembled by placing the polyelectrolyte film (containing cross-linked PILSBC) between Li metal (acting as anode) and the cathode in the cell cases and pressing them by an electric crimper. A small amount of (about 1-2 ml) 1 molar of Li salt and IL was added to each electrode (cathode and anode) to improve contact between electrodes and polyelectrolyte film during the assembly. The cell was allowed to rest for about 24 hours to form a stable interface between the polyelectrolyte film and each electrode.
  • Table 5 presents discharge capacity of cell as a function of crimping pressure using the film of cross-linked PILSBC-1 and "r" value being 0.9.
  • Table 4 Polyelectrolyte Composition with cross-linked PILSBC Cycles Discharge capacity [mAh/g] Cross-linked PILSBC-Li-1.1 5 135.342 10 131.862 15 134.657 20 135.883 25 134.362 30 134.804 35 132.108 40 130.587 Cross-linked PILSBC-Li-1.5 5 130.637 10 131.48 15 132.706 20 131.187 25 128.098 30 124.226 Cross-linked PILSBC-Li-1.10 5 125.147 10 130.294 15 126.421 20 125.687 25 127.696 30 125.785 35 125.442 40 125.097 Cross-linked PILSBC-Li-1.20 5 127.451 10 118.824 15 115.686 20 120.784 25 120.784 30 116.471 35 114.51 40 114.51 Table 5
  • Procedure of example 4 was repeated by replacing NMC811 with Li as a cathode.
  • the obtained cell is a symmetric Li / polyelectrolyte / Li.
  • Galvanostatic stripping / plating cycling of the symmetric cell was evaluated using a battery tester (4200 M, MACCOR) at room temperature and at a constant current density of 0.02 mA cm -1 .
  • the resistances between polyelectrolyte film and Li electrodes (cathode and anode) were recorded by an electrochemical impedance spectroscopy (EIS) for every 10 th polarization cycle at a frequency ranging from 100 kHz to 1 Hz with the amplitude of the voltage disturbance of 10 mV.
  • EIS electrochemical impedance spectroscopy
  • the term “comprising” means including elements or steps that are identified following that term, but any such elements or steps are not exhaustive, and an embodiment can include other elements or steps. Although the terms “comprising” and “including” have been used herein to describe various aspects, the terms “consisting essentially of” and “consisting of” can be used in place of “comprising” and “including” to provide for more specific aspects of the disclosure and are also disclosed.

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005085638A (ja) * 2003-09-09 2005-03-31 Nippon Soda Co Ltd 高分子固体電解質、固体電解質シート及び固体電解質シートの製造方法
US7449518B2 (en) 2006-03-24 2008-11-11 Kraton Polymers U.S. Llc High temperature block copolymers and process for making same
US20150221980A1 (en) * 2013-05-24 2015-08-06 Regents Of The University Of Minnesota Polymer electrolyte membranes
US10022680B2 (en) * 2013-01-14 2018-07-17 Kraton Polymers U.S. Llc Anion exchange block copolymers, their manufacture and their use
CN109786819A (zh) * 2017-11-15 2019-05-21 比亚迪股份有限公司 电解质组合物和聚合物电解质膜以及聚合物电解质及其制备方法和全固态电池及其制备方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005085638A (ja) * 2003-09-09 2005-03-31 Nippon Soda Co Ltd 高分子固体電解質、固体電解質シート及び固体電解質シートの製造方法
US7449518B2 (en) 2006-03-24 2008-11-11 Kraton Polymers U.S. Llc High temperature block copolymers and process for making same
US10022680B2 (en) * 2013-01-14 2018-07-17 Kraton Polymers U.S. Llc Anion exchange block copolymers, their manufacture and their use
US20150221980A1 (en) * 2013-05-24 2015-08-06 Regents Of The University Of Minnesota Polymer electrolyte membranes
CN109786819A (zh) * 2017-11-15 2019-05-21 比亚迪股份有限公司 电解质组合物和聚合物电解质膜以及聚合物电解质及其制备方法和全固态电池及其制备方法

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